Patent Application
20210189856
The present invention relates to the production of hydrogen from subsurface sources.
Hydrocarbon reservoirs are abundant globally and many technologies are known for use in the production of hydrocarbon to surface from these reservoirs, including primary processes as well as secondary recovery processes such as water flooding and chemical flooding to produce additional hydrocarbon.
For heavy oil and extra heavy oil (bitumen), the hydrocarbon is usually too viscous at original reservoir conditions to be produced to surface using conventional methods, and so heavy oil and bitumen are commonly thermally treated to lower the viscosity so that the resource flows more easily in the reservoir and can be produced to the surface.
After heavy oil and bitumen is extracted, it has to be upgraded to synthetic crude oil which in turn is refined into transportation fuels and feedstocks for the petrochemical industry.
However, it is known that the production of hydrocarbon resources results in eventual generation of carbon dioxide since the resources or their products are generally combusted to harvest their energy.
There is thus an ongoing desire to produce fuels such as hydrogen that are more carbon dioxide neutral, which can also be used as chemical feedstock for industries such as upgraders and fertilizer production. However, conventional means of generating hydrogen (e.g., steam methane reforming or electrolysis) are also known to be carbon-intensive or undesirably expensive to implement.
The present invention therefore seeks to provide methods and systems for generating hydrogen, a potentially carbon dioxide neutral energy source and industrial feedstock, from hydrocarbon reservoirs.
According to embodiments of the present invention, in situ gasification, water-gas shift and/or aquathermolysis are employed to produce synthesis gas in the subsurface reservoir, such synthesis gas comprising steam, carbon monoxide, carbon dioxide, and hydrogen, where the carbon oxides are rejected from being produced to the surface by means of a hydrogen-only permeable membrane in the wellbore. The process then produces a gas product largely comprising hydrogen to the surface.
The produced hydrogen is an alternative energy vector that can be produced to the surface from hydrocarbon reservoirs. The produced hydrogen can then be combusted on surface to generate power or heat or consumed in fuel cell devices for production of power or as an industrial feedstock.
In a first broad aspect of the present invention, there is provided a method for producing hydrogen from a hydrocarbon reservoir, the method comprising:
a. providing a well from surface to the reservoir;
b. locating at least one hydrogen-permeable membrane in the well;
c. heating the reservoir to facilitate at least one of gasification, water-gas shift, and aquathermolysis reactions to occur between hydrocarbon and water within the reservoir to generate a gas stream comprising hydrogen; and
d. engaging the gas stream and the at least one hydrogen-permeable membrane, such that the at least one hydrogen-permeable membrane permits passage of only the hydrogen in the gas stream to the surface.
In some exemplary embodiments of the first aspect, the step of heating the reservoir comprises: injecting an oxidizing agent into the reservoir to oxidize at least some of the hydrocarbon within the reservoir; generating electromagnetic or radio-frequency waves with an electromagnetic or radio-frequency antenna placed within the reservoir; injecting a hot material into the reservoir; or generating heat by using a resistance-based (ohmic) heating system located within the reservoir. It will be clear to those skilled in the art that other heating means may be applicable for applications of the present invention.
In some exemplary embodiments, the at least one hydrogen-permeable membrane may comprise at least one of: palladium (Pd), vanadium (V), tantalum (Ta) or niobium (Nb). The at least one hydrogen-permeable membrane may also comprise a palladium-copper alloy, or potentially a palladium-silver alloy. The at least one hydrogen-permeable membrane may comprise a ceramic layer, and most preferably a ceramic layer on the inside or the outside of a palladium-copper alloy. The at least one hydrogen-permeable membrane may comprise a ceramic layer and a non-ceramic layer selected from the group consisting of palladium, vanadium, tantalum, niobium, copper, alloys of these materials, and combinations thereof, and the non-ceramic layer may comprise a palladium-copper alloy.
The at least one hydrogen-permeable membrane is preferably located in the well within the reservoir, but it may also be positioned in the well proximate to the reservoir, or at other points in the well.
In some exemplary embodiments, a porous material is located in the well to support the at least one hydrogen-permeable membrane within the well. The porous material is preferably but not necessarily porous steel.
In some exemplary embodiments of the present invention, methods comprise the further step, after the step of heating the reservoir, of delaying engaging the gas stream and the at least one hydrogen-permeable membrane to allow for further generation of the hydrogen. This step of delaying may comprise delaying for a period in the range of 1 week to 12 months, and most preferably in the range of 1 week to 4 weeks.
In exemplary embodiments where dielectric heating is used for the step of heating the reservoir, electromagnetic radiation may have a frequency in the range of about 60 Hz to 1000 GHz, and preferably in the range of 10 MHz to 10 GHz.
Where a resistance-based (ohmic) heating system is used to heat the reservoir, heating is preferably to temperatures in the range of 200 to 800 degrees C., and most preferably in the range of 400 to 700 degrees C.
In a second broad aspect of the present invention, there is provided a system for recovering hydrogen from a subsurface reservoir, the system comprising:
an apparatus for heating the reservoir to generate a gas stream comprising hydrogen;
a well located in the reservoir; and
a hydrogen-permeable membrane in the well adapted to permit passage therethrough of hydrogen in the gas stream but disallow passage therethrough of other gases in the gas stream, to allow production of the hydrogen through the well to surface.
In some exemplary embodiments of the second aspect, the apparatus for heating the reservoir comprises at least one of an oxidizing-agent injector, an electromagnet, a radio-frequency antenna, and a hot material injector.
The produced hydrogen may be consumed in a fuel electrochemical cell device, combusted to generate steam for power generation or steam for oil recovery, or used as industrial feedstock.
A detailed description of exemplary embodiments of the present invention is given in the following. It is to be understood, however, that the invention is not to be construed as being limited to these embodiments. The exemplary embodiments are directed to particular applications of the present invention, while it will be clear to those skilled in the art that the present invention has applicability beyond the exemplary embodiments set forth herein.
In the accompanying drawings, which illustrate exemplary embodiments of the present invention:
Exemplary embodiments of the present invention will now be described with reference to the accompanying drawings.
Throughout the following description, specific details are set forth in order to provide a more thorough understanding to persons skilled in the art. However, well known elements may not have been shown or described in detail to avoid unnecessarily obscuring the disclosure. The following description of examples of the invention is not intended to be exhaustive or to limit the invention to the precise form of any exemplary embodiment. Accordingly, the description and drawings are to be regarded in an illustrative, rather than a restrictive, sense.
Throughout this specification, numerous terms and expressions are used in accordance with their ordinary meanings. Provided below are definitions of some additional terms and expressions that are used in the description that follows.
“Oil” is a naturally occurring, unrefined petroleum product composed of hydrocarbon components. “Bitumen” and “heavy oil” are normally distinguished from other petroleum products based on their densities and viscosities. “Heavy oil” is typically classified with density of which is between 920 and 1000 kg/m3. “Bitumen” typically has density greater than 1000 kg/m3. For purposes of this specification, the terms “oil”, “bitumen” and “heavy oil” are used interchangeably such that each one includes the other. For example, where the term “bitumen” is used alone, it includes within its scope “heavy oil”.
As used herein, “petroleum reservoir” refers to a subsurface formation that is primarily composed of a porous matrix which contains petroleum products, namely oil and gas. As used herein, “heavy oil reservoir” refers to a petroleum reservoir that is primarily composed of porous rock containing heavy oil. As used herein, “oil sands reservoir” refers to a petroleum reservoir that is primarily composed of porous rock containing bitumen.
“Cracking” refers to the splitting of larger hydrocarbon chains into smaller-chained compounds.
The term “in situ” refers to the environment of a subsurface oil sand reservoir.
In broad aspects, the exemplary methods and systems described herein use oil sand reservoirs as a hydrogen source, both the bitumen and the formation water.
In general, the present specification describes systems and methods to treat oil reservoirs (conventional oil, heavy oil, oil sands reservoirs, carbonate oil reservoirs) to recover hydrogen. The methods include injection of oxygen or an oxygen-rich stream into the reservoir to combust a portion of the hydrocarbons in the reservoir.
In some preferred exemplary embodiments, during injection of the oxidizing agent no fluids are produced to the surface. After the target temperature is achieved in the reservoir, injection stops and during this time the remaining oxygen in the reservoir is consumed and gasification reactions and the water-gas shift reaction takes place. During these reactions, hydrogen is produced within the reservoir. The production well is completed with a hydrogen-only permeable membrane, which when opened for production only produces hydrogen to the surface. After the hydrogen production rate drops below a threshold value, oxygen injection starts once again and the process is repeated multiple times until the overall hydrogen production rate drops below a threshold value. The threshold value can be determined from a minimum hydrogen production rate that is economic which will be set by the costs of oxygen injection, price of hydrogen production, storage, transportation, and consumption (e.g., in a fuel cell for power), and the costs of operation. The hydrogen-only permeable membrane prevents the production of carbon oxides to the surface. Thus, the process yields hydrogen from the hydrocarbons and water that are situated within the reservoir. If needed to enable the desired reactions, water may be injected into the reservoir with the oxygen.
Oxidation of the reservoir fluids by injecting oxygen into the reservoir is one means to generate heat within the reservoir. The reactions that occur in the reservoir at elevated temperatures can include low and high temperature oxidation, pyrolysis (thermal cracking), aquathermolysis (hydrous pyrolysis or thermal cracking reactions in the presence of water), gasification reactions, and the water-gas shift reaction.
Another exemplary system 30 according to the present invention is illustrated in
Another related embodiment is illustrated in
The reactions generate gas which then enables gravity drainage (due to density difference) of hot mobilized oil and steam condensate towards the base of the gasification reaction chamber. Thus, additional source material for further reaction is provided by moving mobilized oil towards the reactive zone above and around the injection well or antenna. This helps with gasification reactions and maintains the 700+ degrees C. zone near the well. The in-well membrane allows hydrogen to pass but holds other gas molecules in the reservoir.
In other embodiments, not illustrated, a single-well configuration could be used wherein oxygen is injected along one part of the well and hydrogen-only production occurs along another part of the well. The well can be vertical, deviated, horizontal or multilateral.
In further non-illustrated embodiments, heating of the reservoir can be done by electromagnetic or radio frequency waves. Alternatively, heating of the reservoir can be done using high pressure, high temperature steam.
The present method can also be used in oil and gas reservoirs where the water content of the reservoir is considered high such that in normal practice, these reservoirs would not be produced for oil or gas, respectively. Methods and system according to the present invention could be used in high water content hydrocarbon reservoirs since hydrogen is sourced not only from the hydrocarbon but also the water within the reservoir. Thus, the methods taught herein may be capable of use in reservoirs where the high water content renders them less valuable than oil saturated reservoirs, converting previously less valuable petroleum reservoirs to valuable energy sources since the hydrogen is sourced from both the petroleum as well as the water in the reservoir.
The present invention relates to treatment of an oil or gas reservoir for production of hydrogen from the hydrocarbon and water within the reservoir. The treatment includes heating the reservoir to enable gasification and water-gas shift reaction to produce hydrogen within the reservoir and then using a hydrogen-only production well, equipped with a hydrogen membrane, to produce hydrogen from the reservoir.
High water content in oil and gas reservoirs is typically thought to be disadvantageous for oil or gas production. However, it has been found that high water content may be a benefit for the production of hydrogen since water supplies hydrogen due to the water-gas shift reaction. It has been found that many of the reactions that produce hydrogen source the hydrogen from the water in the reservoir—under the temperatures of the reactions, the formation water is converted to steam which then participates in the steam reforming reactions with the hydrocarbons in the reservoir.
Following is further detailed description regarding certain exemplary embodiments of the present invention.
In certain exemplary embodiments, the reservoir is heated to a temperature where gasification and water-gas shift reactions take place between the oil and water within the reservoir.
The heat can be delivered to the reservoir through a variety of methods commonly known in the art. Typical methods used in the art include a combustion step where oxygen is injected into the reservoir for a period of time where a portion of the hydrocarbon is combusted to generate heat within the reservoir to achieve temperatures on the order of 400 to 700 degrees C. Other modes of heating including electromagnetic or radio frequency based heating. Other modes of heating include injecting hot materials into the reservoir.
After the heat is injected to the reservoir, if done by combustion, oxygen injection is stopped and the chemical reactions are allowed to continue within the reservoir at the elevated temperature achieved by the combustion step. If heated by electromagnetic heating, then this heating can continue to keep the reservoir at the desired reaction temperature.
During the period of time at the which the reservoir is at elevated temperature, gasification and water-gas shift and aquathermolysis reactions may occur with consequent generation of hydrogen, hydrogen sulphide, carbon monoxide, carbon dioxide, and steam (water vapour), and possibly other gases. As the reactions occur in the reservoir, the gas components collect within the reservoir pore spaces and any fractures or other void spaces in the reservoir.
After enough time has elapsed for the generation of hydrogen, the hydrogen is produced from the reservoir through the hydrogen-only membranes within the production well. In this manner, the hydrogen sulphide, carbon monoxide, carbon dioxide, steam, and other gas components remain in the reservoir while the hydrogen alone is produced to surface. Since hydrogen is removed from the reservoir, this promotes the reactions to generate more hydrogen.
For the hydrogen-only membrane to be placed in the production well, metallic membranes, for example, constructed from palladium (Pd), vanadium (V), tantalum (Ta) or niobium (Nb), are mechanically robust but with limited ranges of optimal performance with respect to temperature. These membranes work by a solubility-diffusion mechanism, with the hydrogen dissolving in the membrane material and diffusing to the other side where it is released; this mechanism yields hydrogen flux (moles transport rate per unit area) proportional to the square root of the pressure. To illustrate, vanadium and titanium permeability to hydrogen drops at high temperatures and also forms metal oxide layers that prevent efficient hydrogen separation. Pd-based membranes have the advantage since their hydrogen permeability rises with increasing temperature. However, Pd membranes are poisoned by hydrogen sulfide (H2S) and carbon monoxide (CO) which are created by aquathermolysis when steam and oil, e.g. bitumen, are contacted at elevated temperatures. This can be countered by using Pd-Copper alloys. For cost reduction, multilayer membranes consisting of Pd—Cu alloy and V, Ta, and Nb could be constructed. Other alloys such as palladium-silver alloys may also be useful for certain embodiments of the present invention.
Ceramic membranes are inert to H2S and CO and can be used at temperatures achieved by in situ gasification processes. Microporous ceramic membranes for hydrogen separation have several advantages over metallic membranes: the flux is directly proportional to the pressure; the permeability of ceramic microporous membranes rises significantly with temperature; and the cost of the raw materials for ceramic membranes is much less than that of metallic membranes. Since they are porous, they tend not to produce pure hydrogen although they can be hydrogen-selective with relatively high hydrogen permeability. In some embodiments, the membrane can have a ceramic layer to not only provide ability to separate hydrogen from gas components generated from the reactions but to also strengthen the membrane.
In some embodiments, the hydrogen membrane is configured to be highly selective to hydrogen (especially if the hydrogen gas is to be used for power generation from a fuel cell at surface), highly permeable to hydrogen, capable of withstanding heating up to 700 degrees C., able to withstand H2S and CO gas, robust mechanically given the issues of placing the membranes in the well, and/or capable of being manufactured with diameters and lengths that can fit in wells (between 20-30 cm in diameter and 700-1000 m in length). In some embodiments, the membranes can also withstand the partial oxidation stage which will consume carbon and other solid buildup on the exterior surface of the composite membrane.
Turning now to
If the heating is done in a cyclic manner, for example, from in situ combustion, then after the temperature of the reservoir has dropped such that the gasification, water-gas shift, and aquathermolysis reaction rates have dropped so that hydrogen production drops below a threshold value, then a new cycle of oxygen injection and consequent in situ combustion will start leading to renewed heating of the reservoir. Thereafter, Steps A to C above are repeated. If continuous heating is done by oxidization agent injection or electromagnetic or radio frequency or resistive heating methods, then continuous hydrogen production can occur from the reservoir.
The above examples illustrate exemplary methods of conducting in situ gasification reactions within a reservoir where a membrane is used in the production well to produce hydrogen to the surface.
The hydrogen generated from the methods taught here can be used in fuel cells at surface to generate power, or combusted to produce steam which can be used to generate power or for other in situ oil recovery processes, or sold as industrial feedstock.
As will be clear from the above, those skilled in the art would be readily able to determine obvious variants capable of providing the described functionality, and all such variants and functional equivalents are intended to fall within the scope of the present invention.
Unless the context clearly requires otherwise, throughout the description and the claims:
Words that indicate directions such as “vertical”, “transverse”, “horizontal”, “upward”, “downward”, “forward”, “backward”, “inward”, “outward”, “vertical”, “transverse”, “left”, “right”, “front”, “back”, “top”, “bottom”, “below”, “above”, “under”, and the like, used in this description and any accompanying claims (where present) depend on the specific orientation of the apparatus described and illustrated. The subject matter described herein may assume various alternative orientations. Accordingly, these directional terms are not strictly defined and should not be interpreted narrowly.
Specific examples of methods and systems have been described herein for purposes of illustration. These are only examples. The technology provided herein can be applied to contexts other than the exemplary contexts described above. Many alterations, modifications, additions, omissions and permutations are possible within the practice of this invention. This invention includes variations on described embodiments that would be apparent to the skilled person, including variations obtained by: replacing features, elements and/or acts with equivalent features, elements and/or acts; mixing and matching of features, elements and/or acts from different embodiments; combining features, elements and/or acts from embodiments as described herein with features, elements and/or acts of other technology; and/or omitting combining features, elements and/or acts from described embodiments.
The foregoing is considered as illustrative only of the principles of the invention. The scope of the claims should not be limited by the exemplary embodiments set forth in the foregoing, but should be given the broadest interpretation consistent with the specification as a whole.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CA2017/050135 | 2/7/2017 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62292556 | Feb 2016 | US |
